CN113136160B - Waterborne polyurethane adhesive and preparation method thereof - Google Patents
Waterborne polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN113136160B CN113136160B CN202110425587.0A CN202110425587A CN113136160B CN 113136160 B CN113136160 B CN 113136160B CN 202110425587 A CN202110425587 A CN 202110425587A CN 113136160 B CN113136160 B CN 113136160B
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Abstract
The invention belongs to the technical field of adhesives, and particularly relates to a water-based polyurethane adhesive and a preparation method thereof. The preparation process comprises the following steps: firstly, polymerizing polyester polyol, polyether, diisocyanate and a micromolecular chain extender under the action of a catalyst, adding acetone for viscosity reduction, then adding an amino-terminated silane coupling agent, a hydrophilic chain extender, an amine chain extender and a chelating agent, and continuously reacting to obtain a waterborne polyurethane prepolymer; adding water into the prepolymer, shearing and emulsifying at a high speed, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion; and finally, adding a defoaming agent, a thickening agent and a curing agent into the emulsion to prepare the waterborne polyurethane adhesive. The aqueous polyurethane adhesive has high solid content, good calcium ion stability and outstanding bonding strength, further improves the water resistance and heat resistance of the product, and can be used in the shoe making industry. Finally, the acetone is removed under reduced pressure, and can be recycled, so that the environmental pollution is reduced, the method belongs to clean production, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a water-based polyurethane adhesive and a preparation method thereof.
Background
China is a big shoe-making country in the world, the shoe yield is over 135 hundred million pairs in 2018, and the required adhesive dosage reaches 50 million tons per year. At present, more adhesives used are solvent adhesives, organic solvents have good swelling property on substrates such as plastics, leather, rubber and the like, active ingredients in the adhesives can permeate into materials, the adhesives show excellent bonding performance, and meanwhile, the construction time can be adjusted according to the volatilization speeds of different solvents. There are two broad categories of solvent-based adhesives that are most used, namely neoprene and Polyurethane (PU) adhesives. The neoprene adhesive has strong water resistance, oil resistance, solvent resistance, acid and alkali resistance and ageing resistance, and simultaneously has excellent bonding strength and low cost, so the neoprene adhesive is still an indispensable important adhesive in the shoe manufacturing industry of China. However, chloroprene rubber is not resistant to penetration of plasticizers, and has poor adhesion to novel shoe substrates such as thermoplastic rubber, soft polyvinyl chloride and polyurethane synthetic leather, so chloroprene rubber is gradually replaced by polyurethane adhesives.
The water-based polyurethane adhesive takes water as a dispersion medium, is milky blue, is transparent after being cured, has the characteristics of adjustable hardness, low temperature resistance, good flexibility, high bonding strength and the like as a solvent-based polyurethane adhesive, and has three remarkable advantages compared with the traditional solvent-based adhesive: 1. the environment is protected, no or little VOC is contained, and no harm is caused to human bodies and ecological environment; 2. the fire-fighting agent is not flammable and explosive, is safe to store and has no fire-fighting hidden danger; 3. the solid content is high and is 3-4 times of that of the traditional solvent-based product, the later-stage bonding effect higher than that of the solvent-based product can be achieved, a large number of shoe materials can be brushed with glue once, and the cost performance is higher. Therefore, the waterborne polyurethane adhesive can reduce environmental pollution from the source, has the characteristics of environmental protection, safety and high cost performance, and is beneficial to transformation and upgrading of the shoemaking industry.
However, the waterborne polyurethane contains hydrolyzable groups, which are easily hydrolyzed when stored under ambient conditions, as opposed to solvent-borne polyurethanes, and the presence of metal ions in the system (e.g., metal ions introduced in the catalyst) also promotes hydrolysis of the hydrolyzable groups on the waterborne polyurethane. Therefore, the aqueous polyurethane adhesive often has the problems of low initial adhesion, poor water resistance, short viscosity maintaining time and the like; in addition, the existing sulfonate type waterborne polyurethane often contains more sulfonates, and the ionic stability of the existing sulfonate type waterborne polyurethane is relatively weak.
Disclosure of Invention
The invention aims to provide a preparation method of a waterborne polyurethane adhesive by improving a polymerization process of waterborne polyurethane aiming at the problems of low initial adhesion, poor water resistance, weak ionic stability and the like in the prior art. The water-soluble chelating agent is added to be complexed with metal ions in a system to form a stable compound, so that the stable compound does not promote the hydrolysis of polyurethane any more; by introducing siloxane, the water resistance and the heat resistance of the waterborne polyurethane are improved; a small amount of hydrophilic polyether is added to replace part of hydrophilic groups of sulfonate, so that the content of sulfonate is reduced, and the water-based polyurethane adhesive with excellent stability is further prepared. The obtained product does not contain organic solvent basically, is environment-friendly and safe, and has outstanding bonding strength, water resistance, heat resistance and ionic stability.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the water-based polyurethane adhesive comprises the following steps:
in the first step, polymerization: firstly, 80 parts by mass of polyester polyol and 1-2 parts by mass of polyether are put into a reactor, vacuum dehydration is carried out for 2 hours at the temperature of 100-120 ℃, after the dehydration is finished, the temperature is reduced to 50-60 ℃, then 10-20 parts by mass of acetone, 6-12 parts by mass of diisocyanate, 0.01-0.1 part by mass of micromolecular chain extender and 0.01-0.02 part by mass of organic metal catalyst are added into the reactor, the reaction is carried out for 2.5-4 hours at the temperature of 80 ℃, sampling is carried out, the NCO value is measured by adopting a di-n-butylamine method, the temperature of the reactor is reduced to be below 55 ℃ after the index is qualified, 80-100 parts by mass of acetone are added to reduce the viscosity, then 0.1-0.8 part by mass of terminal aminosilane coupling agent KH792, 0.5-2 parts by mass of hydrophilic chain extender, 0.1-2 parts by mass of amine chain extender and 0.1-0.2 parts by mass of chelating agent are put into the reactor, reacting for 20-30 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100-150 parts by mass of deionized water into the waterborne polyurethane prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: adding 0.02 part by mass of defoaming agent into 100 parts by mass of waterborne polyurethane emulsion, stirring for 5 minutes, adding 0.15 part by mass of thickening agent, stirring for 10 minutes, then adding 5 parts by mass of curing agent, and uniformly stirring to obtain the waterborne polyurethane adhesive.
Further, the polyester polyol in the first step is any one or any combination of polycaprolactone polyol, polycarbonate polyol and polyadipate polyol, and is preferably polybutylene adipate.
Further, the polyether in the first step is one or a combination of hydrophilic polypropylene glycol monomethyl ether and polyethylene glycol monomethyl ether, preferably polyethylene glycol monomethyl ether.
Further, the diisocyanate in the first step is any one of isophorone diisocyanate and hexamethylene diisocyanate in any combination, and preferably the combination of isophorone diisocyanate and hexamethylene diisocyanate.
Further, the small molecular chain extender in the first step is any one or any combination of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and sorbitol glycol, and 1, 4-butanediol is preferred.
Further, the organic metal catalyst in the first step is any one or any combination of organic bismuth, organic zinc, organic zirconium and bismuth-zinc alloy catalyst, and dibutyltin dilaurate is preferred.
Further, the hydrophilic chain extender in the first step is any one or any combination of dimethylolbutyric acid, dimethylolpropionic acid, dihydroxy sulfonate and diaminosulfonate, and preferably sodium ethylene diamine ethane sulfonate.
Further, the amine chain extender in the first step is any one or any combination of ethylenediamine, isophoronediamine and hydroxyethylethylenediamine, preferably isophoronediamine.
Further, the chelating agent in the first step is any one or any combination of ethylenediamine tetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate, and sodium pyrophosphate is preferred.
The invention has the following remarkable advantages:
the invention provides a preparation method of a waterborne polyurethane adhesive, which is characterized in that a water-soluble chelating agent is added to be complexed with metal ions in a system to form a stable compound, so that the hydrolysis of polyurethane is not promoted any more; by introducing siloxane, the water resistance and the heat resistance of the waterborne polyurethane are improved; a small amount of hydrophilic polyether is added to replace part of hydrophilic groups of sulfonate, so that the content of sulfonate is reduced, and the water-based polyurethane adhesive with excellent stability is further prepared. The obtained product does not contain organic solvent basically, is environment-friendly and safe, and has outstanding bonding strength, water resistance, heat resistance and ionic stability.
The aqueous polyurethane adhesive has high solid content, good calcium ion stability and outstanding bonding strength, further improves the water resistance and heat resistance of the product, and can be used in the shoe making industry. Finally, the acetone is removed under reduced pressure, and can be recycled, so that the environmental pollution is reduced, the method belongs to clean production, and the production cost is reduced.
Detailed Description
The invention is further illustrated below:
example 1
In the first step, polymerization: weighing 80g of polybutylene adipate and 1.6 g of polyethylene glycol monomethyl ether, adding the weighed materials into a four-necked flask provided with a thermometer and a stirring paddle, removing water in a vacuum environment at 100 ℃ for 2 hours, cooling to 50 ℃ after the water is removed, adding 15 g of acetone, 4.7 g of isophorone diisocyanate, 7.1 g of hexamethylene diisocyanate, 0.05 g of 1, 4-butanediol and 0.02 g of dibutyltin dilaurate into a reactor, gradually heating to 80 ℃ for reaction for 3 hours, sampling, measuring an NCO value by adopting a di-n-butylamine method, reducing the temperature of the reactor to be below 55 ℃ after the index is qualified, adding 85 g of acetone to reduce the viscosity, then adding 0.11 g of an amino-terminated silane coupling agent KH792, 0.8 g of ethylenediamine sodium ethanesulfonate, 0.6 g of isophorone diamine and 0.1 g of sodium pyrophosphate into the reactor, reacting for 20 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100 g of deionized water into the prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: and adding 0.02 g of defoaming agent into 100 g of aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 g of thickening agent, stirring for 10 minutes, adding 5 g of curing agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
Example 2
In the first step, polymerization: firstly weighing 80g of poly (hexanediol neopentyl glycol adipate) and 1 g of polyethylene glycol monomethyl ether, adding the materials into a four-necked flask provided with a thermometer and a stirring paddle, removing water in a vacuum environment at 100 ℃ for 2 hours, cooling to 50 ℃ after the water removal is finished, then adding 15 g of acetone, 5 g of isophorone diisocyanate, 7 g of hexamethylene diisocyanate, 0.04 g of 1, 4-butanediol and 0.02 g of dibutyltin dilaurate into a reactor, gradually heating to 80 ℃ for reaction for 3 hours, sampling, measuring an NCO value by a di-n-butylamine method, reducing the temperature of the reactor to below 55 ℃ after indexes are qualified, adding 85 g of acetone to reduce the viscosity, then adding 0.22 g of an aminosilane coupling agent KH792, 1.2 g of ethylenediamine sodium sulfonate, 0.6 g of isophorone diamine and 0.2 g of sodium pyrophosphate into the reactor, reacting for 20 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100 g of deionized water into the prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: and adding 0.02 g of defoaming agent into 100 g of aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 g of thickening agent, stirring for 10 minutes, adding 5 g of curing agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
Example 3
In the first step, polymerization: weighing 80g of poly (hexanediol neopentyl glycol adipate) and 1.2 g of polypropylene glycol monomethyl ether, adding the materials into a four-necked flask provided with a thermometer and a stirring paddle, carrying out vacuum dehydration for 2 hours at the temperature of 100 ℃, cooling to 50 ℃ after the dehydration is finished, adding 15 g of acetone, 4.7 g of isophorone diisocyanate, 7.1 g of hexamethylene diisocyanate, 0.05 g of 1, 6-hexanediol and 0.02 g of dibutyltin dilaurate into a reactor, gradually heating to 80 ℃ for reaction for 3 hours, sampling, measuring an NCO value by adopting a di-n-butylamine method, reducing the temperature of the reactor to be below 55 ℃ after the indexes are qualified, adding 85 g of acetone to reduce the viscosity, then adding 0.44 g of a terminal aminosilane coupling agent KH792, 1.6 g of sodium ethylenediamine sulfonate, 0.4 g of isophorone diamine and 0.1 g of sodium pyrophosphate into the reactor, reacting for 20 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100 g of deionized water into the prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: and adding 0.02 g of defoaming agent into 100 g of aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 g of thickening agent, stirring for 10 minutes, adding 5 g of curing agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
Example 4
The first step, polymerization: weighing 80g of polytetrahydrofuran and 1.2 g of polypropylene glycol monomethyl ether, adding the polytetrahydrofuran and the polypropylene glycol monomethyl ether into a four-necked flask provided with a thermometer and a stirring paddle, removing water in a vacuum environment at 100 ℃ for 2 hours, cooling to 50 ℃ after the dehydration is finished, adding 15 g of acetone, 4.7 g of isophorone diisocyanate, 7.1 g of hexamethylene diisocyanate, 0.05 g of 1, 4-butanediol and 0.02 g of dibutyltin dilaurate into a reactor, gradually heating to 80 ℃ for reaction for 3 hours, sampling, measuring an NCO value by adopting a di-n-butylamine method, reducing the temperature of the reactor to be below 55 ℃ after the indexes are qualified, adding 85 g of acetone to reduce the viscosity, then adding 0.66 g of an amino-terminated silane coupling agent KH792, 0.2 g of sodium ethylene diamine ethanesulfonate, 0.8 g of isophorone diamine and 0.2 g of tetrasodium ethylenediamine tetraacetate into the reactor, reacting for 20 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100 g of deionized water into the prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: and adding 0.02 g of defoaming agent into 100 g of aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 g of thickening agent, stirring for 10 minutes, adding 5 g of curing agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
Comparative example 1
In the first step, polymerization: firstly, 80g of polybutylene adipate is weighed and added into a four-neck flask provided with a thermometer and a stirring paddle, vacuum dewatering for 2 hours at the temperature of 100 ℃, after dewatering, cooling to 50 ℃, adding 15 g of acetone, 4.7 g of isophorone diisocyanate, 7.1 g of hexamethylene diisocyanate, 0.05 g of 1, 4-butanediol and 0.02 g of dibutyltin dilaurate into a reactor, gradually heating to 80 ℃ for reaction for 3 hours, sampling, measuring the NCO value by adopting a di-n-butylamine method, cooling the reactor to below 55 ℃ after the index is qualified, adding 85 g of acetone to reduce the viscosity, then 0.66 g of terminal aminosilane coupling agent KH792, 2 g of ethylenediamine sodium ethanesulfonate and 0.4 g of isophorone diamine are added into the reactor and react for 20 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100 g of deionized water into the prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: and adding 0.02 g of defoaming agent into 100 g of aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 g of thickening agent, stirring for 10 minutes, adding 5 g of curing agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
Comparative example 2
In the first step, polymerization: weighing 80g of polybutylene adipate and 0.8 g of polyethylene glycol monomethyl ether, adding the weighed materials into a four-necked flask provided with a thermometer and a stirring paddle, carrying out vacuum dehydration for 2 hours in an environment with the temperature of 100 ℃, cooling to 50 ℃ after the dehydration is finished, adding 15 g of acetone, 4.7 g of isophorone diisocyanate, 7.1 g of hexamethylene diisocyanate, 0.05 g of 1, 4-butanediol and 0.02 g of dibutyltin dilaurate into a reactor, gradually heating to 80 ℃ for reaction for 3 hours, sampling, measuring an NCO value by adopting a di-n-butylamine method, reducing the temperature of the reactor to be below 55 ℃ after the indexes are qualified, adding 85 g of acetone to reduce the viscosity, then adding 2 g of sodium ethylenediamine sulphonate and 1 g of isophorone diamine into the reactor, and reacting for 20 minutes to obtain a waterborne polyurethane prepolymer;
and step two, emulsification: adding 100 g of deionized water into the prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
step three, glue mixing: and adding 0.02 g of defoaming agent into 100 g of aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 g of thickening agent, stirring for 10 minutes, adding 5 g of curing agent, and uniformly stirring to obtain the aqueous polyurethane adhesive.
Then, the aqueous polyurethane adhesives prepared in the above examples and comparative examples were subjected to mechanical property tests for adhesion between rubber substrates, and water absorption of the adhesive films was measured, as shown in the following table:
TABLE 1 Performance of waterborne polyurethane adhesives and films
The polyether addition amount of comparative example 1 and comparative example 2 is less than 1 g in the examples, the sulfonate amount exceeds 1.8 g, and the calcium ion stability test is not passed, which shows that the introduction of the hydrophilic polyether to replace part of the sulfonate can effectively improve the ionic stability.
The comparative examples 1 and 2, in which no chelating agent was added, also had a higher measured water absorption than the other examples in which the chelating agent was added, indicating that the introduction of the chelating agent was effective in improving the water resistance.
Comparative example 2, in which no siloxane was added, had a water absorption rate measured higher than 3.27% of that of comparative example 1, indicating that the introduction of siloxane was also effective in improving its water resistance.
The data show that the aqueous polyurethane adhesive has high solid content, good calcium ion stability and outstanding bonding strength, the water resistance and heat resistance can be effectively improved by introducing the organic silicon, but the organic silicon accounts for 0.1-0.2% of the total mass of the aqueous polyurethane prepolymer, and the crystallization performance is reduced rapidly and adverse effect is brought by excessive introduction. Meanwhile, when the dosage of the polyether exceeds 1 g and the dosage of the ethylenediamine ethanesulfonic acid sodium salt does not exceed 1.8 g, the calcium ion stability can be detected.
The implementation of the invention is characterized in that the introduction of the terminal amino silane coupling agent further improves the water resistance and heat resistance of the product; the chelating agent is introduced, so that the promotion effect of metal ions on hydrolysis is reduced, and the water resistance of the product is improved; polyethylene glycol monomethyl ether is introduced, and the polyethylene glycol monomethyl ether has strong hydrophilicity and can replace partial sulfonate, so that the ionic stability of the product is improved, and the water-based polyurethane adhesive with excellent performance is prepared; finally, the acetone is removed under reduced pressure, and can be recycled, so that the environmental pollution is reduced, the method belongs to clean production, and the production cost is reduced.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the appended claims.
Claims (8)
1. The preparation method of the water-based polyurethane adhesive is characterized by comprising the following steps:
(1) polymerization: firstly, 80 parts by mass of polyester polyol and 1-2 parts by mass of polyether are put into a reactor, vacuum dehydration is carried out for 2 hours at the temperature of 100-120 ℃, after the dehydration is finished, the temperature is reduced to 50-60 ℃, then 10-20 parts by mass of acetone, 6-12 parts by mass of diisocyanate, 0.01-0.1 part by mass of micromolecule chain extender and 0.01-0.02 part by mass of organic metal catalyst are added into the reactor, the temperature is gradually raised to 80 ℃ for reaction for 2.5-4 hours, sampling is carried out, the NCO value is measured, the temperature of the reactor is reduced to be below 55 ℃ after the index is qualified, 80-100 parts by mass of acetone is added for reducing the viscosity, then 0.1-0.8 part by mass of terminal amino silane coupling agent KH792, 0.1-2 parts by mass of hydrophilic agent, 0.1-2 parts by mass of amine chain extender and 0.1-0.2 part by mass of chelating agent are put into the reactor, reacting for 20-30 minutes to obtain a waterborne polyurethane prepolymer;
(2) emulsification: adding 100-150 parts by mass of deionized water into the waterborne polyurethane prepolymer, carrying out high-speed shearing emulsification for 1 hour, and removing acetone under reduced pressure to obtain a waterborne polyurethane emulsion;
(3) glue mixing: adding 0.02 part by mass of a defoaming agent into 100 parts by mass of the aqueous polyurethane emulsion, stirring for 5 minutes, adding 0.15 part by mass of a thickening agent, stirring for 10 minutes, then adding 5 parts by mass of a curing agent, and uniformly stirring to obtain an aqueous polyurethane adhesive;
the polyether in the step (1) is one or the combination of hydrophilic polypropylene glycol monomethyl ether and polyethylene glycol monomethyl ether;
the chelating agent in the step (1) is any one or any combination of ethylenediamine tetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate.
2. The method of claim 1, wherein: the polyester polyol in the step (1) is any one or any combination of polycaprolactone polyol, polycarbonate polyol and polyadipate polyol.
3. The method of claim 1, wherein: the diisocyanate in the step (1) is any one or any combination of isophorone diisocyanate, hexamethylene diisocyanate and methylcyclohexyl isocyanate.
4. The method of claim 1, wherein: the micromolecular chain extender in the step (1) is any one or any combination of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and sorbitol glycol.
5. The method of claim 1, wherein: the organic metal catalyst in the step (1) is any one or any combination of organic bismuth, organic tin, organic zirconium and bismuth-zinc alloy catalyst.
6. The method of claim 1, wherein: the hydrophilic chain extender in the step (1) is any one or any combination of dimethylolbutyric acid, dimethylolpropionic acid, dihydroxy sulfonate and diamino sulfonate.
7. The method for preparing the waterborne polyurethane adhesive according to claim 1, wherein: the amine chain extender in the step (1) is any one or any combination of ethylenediamine, isophorone diamine and hydroxyethyl ethylenediamine.
8. The aqueous polyurethane adhesive prepared by the process according to any one of claims 1 to 7.
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